Herbicidal cyclohexanedione derivatives

ABSTRACT

The present invention relates to compounds of Formula (I), wherein R1, R2, R3, R4 and G are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I), to their use for controlling weeds, in particular in crops of useful plants.

The present invention relates to novel herbicidal cyclohexanedionecompounds, to processes for their preparation, to herbicidalcompositions which comprise the novel compounds, and to their use forcontrolling weeds.

Herbicidal cyclic dione compounds substituted by a phenyl which hasvarious substituents are disclosed in, for example, WO2008/110308.Herbicidal propynyl-phenyl compounds are disclosed in WO2015/197468. Thepresent invention relates to novel herbicidal cyclohexanedionederivatives with improved properties.

Thus, according to the present invention there is provided a compound ofFormula (I)

wherein

-   -   R¹ is selected from methyl, ethynyl, 1-propynyl, phenyl and a 5        or 6 membered heteroaryl which comprises one or two nitrogen        heteroatoms, said phenyl and heteroaryl optionally substituted        by one or two R¹⁵ substituents;    -   R² is ethyl or chloro;    -   R³ is selected from the group consisting of methyl, ethyl,        methoxy and chloro;    -   R⁴ is selected from the group consisting of C₁-C₄alkyl,        C₁-C₄alkoxy-, C₁-C₄haloalkyl, —C(═O)C₁-C₄alkyl,        —C(═O)C₁-C₄haloalkyl, —S(O)_(n)C₁-C₆alkyl,        —S(O)_(n)C₁-C₆haloalkyl, —S(O)_(n)—(CH₂)_(n)—C₃-C₆cycloalkyl,        —S(O)_(n)C(R¹¹)R¹²R¹³, —C(O)H, —C(O)—(CH₂)_(n)—C₃-C₆cycloalkyl,        —C(O)C(R¹¹)R¹²R¹³, —C(O)C₂-C₄alkenyl, —C(O)(CR⁹R¹⁰)CN,        —C(O)(CR⁹R¹⁰)(CR⁹R¹⁰)CN, —C(O)CH₂C(O)—C₁-C₆alkyl,        —C(O)CH₂OC(O)—C₁-C₆alkyl, —C(O)OC₁-C₆alkyl,        —C(O)OC₁-C₆haloalkyl, —C(O)(CH₂)_(n)S(O)_(n)C₁-C₆alkyl,        —C(O)C₁-C₃alkoxyC₁-C₆alkyl, —C(O)C₁-C₃alkoxyC₂-C₆alkenyl,        —C(O)C₁-C₃alkoxyC₂-C₆alkynyl, —C(O)C₁-C₃alkoxyC₁-C₆haloalkyl,        —C(O)C₁-C₃alkoxyC₃-C₆cycloalkyl, —C(O)OC₁-C₃alkoxyC₁-C₆alkyl,        —C(O)C₁-C₃alkoxyC₁-C₃alkoxyC₁-C₆alkyl, —C(O)(CH₂)_(n)NR⁵R⁶,        —C(O)—(CH₂)_(n)—NR⁷C(O)R⁸, —C(O)—(CH₂)_(n)—O—N═CR⁵R⁵, —CN,        —S(O)₂NR¹⁶R¹⁷, —S(O)(═NR¹⁸)R¹⁹, —C(O)C(O)R²⁰,        —C(O)C(R²³)═N—O—R²⁴ or —C(O)C(R²³)═N—NR²⁵R²⁶, —(CH₂)_(n)-phenyl,        —C(O)—(CH₂)_(n)-phenyl, —S(O)_(n)—(CH₂)_(n)-phenyl,        -heterocyclyl, —O(O)—(CH₂)_(n)-heterocyclyl,        —C(O)(CH₂)_(n)O—(CH₂)_(n)-heterocyclyl,        —S(O)_(n)—(CH₂)_(n)-heterocyclyl, wherein each heterocyclyl is a        5- or 6-membered heterocyclyl which may be aromatic, saturated        or partially saturated and can contain from 1 to 4 heteroatoms        each independently selected from the group consisting of oxygen,        nitrogen and sulphur, and wherein said heterocyclyl or phenyl        groups are optionally substituted by one, two or three        substituents independently selected from the group consisting of        C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₂-C₃alkenyl,        C₂-C₃alkynyl, halogen, cyano and nitro;    -   R⁵ is independently selected from the group consisting of        hydrogen and C₁-C₆ alkyl;    -   R⁶ is selected from the group consisting of hydrogen,        C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆haloalkyl,        hydroxyl-, C₁-C₆alkoxy, C₃-C₆ cycloalkyl,        —C₁-C₄alkoxyC₁-C₆alkyl, —C₁-C₃alkoxyC₁-C₆haloalkyl,        —(CR⁹R¹⁰)C₁-C₆haloalkyl, —(CR⁹R¹⁰)C(O)NR⁵R⁵, phenyl, -pyridyl,        wherein the phenyl and pyridyl are optionally substituted by        one, two or three substituents independently selected from the        group consisting of C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy,        C₂-C₃ alkenyl, C₂-C₃ alkynyl, halogen, cyano and nitro; or    -   R⁵ and R⁶ together form —CH₂CH₂OCH₂CH₂—; and    -   R⁷ is selected from the group consisting of hydrogen and C₁-C₆        alkyl;    -   R⁸ is selected from the group consisting of hydrogen, C₁-C₆        alkyl, C₁-C₆ alkoxy, C₃-C₆ cycloalkyl, phenyl, -pyridyl, wherein        the phenyl and pyridyl are optionally substituted by one, two or        three substituents independently selected from the group        consisting of C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₂-C₃        alkenyl, C₂-C₃ alkynyl, halogen, cyano and nitro;    -   R⁹ is hydrogen or methyl;    -   R¹⁰ is hydrogen or methyl; or    -   R⁹ and R¹⁹ together form —CH₂CH₂—; and    -   R¹¹ is hydrogen or methyl;    -   R¹² is selected from the group consisting of hydrogen, C₁-C₆        alkyl, hydroxyl and C₁-C₆ alkoxy-;    -   R¹³ is selected from the group consisting of hydrogen, C₁-C₆        alkyl, hydroxyl and C₁-C₆ alkoxy; or    -   R¹² and R¹³ together form —CH₂—X—CH₂—; and    -   X is selected from the group consisting of O, S and N—R¹⁴;    -   R¹⁴ is selected from the group consisting of hydrogen, C₁-C₃        alkyl and C₁-C₃ alkoxy-;    -   R¹⁵ is independently selected from the group consisting of C₁-C₄        alkyl, C₁-C₄ haloalkyl, cyano and halogen;    -   R¹⁶ is hydrogen or C₁-C₆alkyl; and    -   R¹⁷ is selected from the group consisting of hydrogen,        C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆ alkoxy-C₁-C₃alkyl-,        —C(O)C₁-C₆alkyl, —C(O)OC₁-C₆alkyl and CH₂CN; or    -   R¹⁶ and R¹⁷ together form —CH₂CH₂OCH₂CH₂—, —CH₂CH₂S(O)₂CH₂CH₂—;    -   R¹⁸ is hydrogen or C₁-C₆alkyl;    -   R¹⁹ is selected from the group consisting of hydrogen, C₁-C₆        alkyl, C₁-C₆ alkoxy, C₃-C₆cycloalkyl, phenyl, -pyridyl, wherein        the phenyl and pyridyl are optionally substituted by one, two or        three substituents independently selected from the group        consisting of C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₂-C₃        alkenyl, C₂-C₃ alkynyl, halogen, cyano and nitro;    -   R²⁰ is selected from the group consisting of C₁-C₆alkyl,        C₁-C₆haloalkyl, C₁-C₆alkoxy-, C₁-C₆haloalkoxy, —NR²¹R²², phenyl        and -pyridyl, wherein the phenyl and pyridyl are optionally        substituted by one, two or three substituents independently        selected from the group consisting of C₁-C₃ alkyl, C₁-C₃        haloalkyl, C₁-C₃ alkoxy, C₂-C₃ alkenyl, C₂-C₃ alkynyl, halogen,        cyano and nitro;    -   R²¹ is selected from the group consisting of hydrogen, C₁-C₆        alkyl, C₁-C₆ alkoxy, C₁-C₆alkoxyC₁-C₃alkyl-, C₃-C₆ cycloalkyl,        C₁-C₆haloalkyl- and C₁-C₆haloalkoxy-, —C(O)C₁-C₆alkyl, phenyl,        -pyridyl, wherein the phenyl and pyridyl are optionally        substituted by one, two or three substituents independently        selected from the group consisting of C₁-C₃ alkyl, C₁-C₃        haloalkyl, C₁-C₃ alkoxy, C₂-C₃ alkenyl, C₂-C₃ alkynyl, halogen,        cyano and nitro;    -   R²² is hydrogen or C₁-C₆alkyl; or    -   R²¹ and R²² together form —CH₂CH₂OCH₂CH₂—;    -   R²³ is selected from the group consisting of hydrogen,        C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy- and C₁-C₆haloalkoxy-;    -   R²⁴ is selected from the group consisting of hydrogen,        C₁-C₆alkyl, C₁-C₆alkoxyC₁-C₃alkyl-, C₃-C₆cycloalkyl, —CH₂CN,        tetrahydropyranyl-, phenyl and -pyridyl, wherein the phenyl and        pyridyl are optionally substituted by one, two or three        substituents independently selected from the group consisting of        C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₂-C₃alkenyl,        C₂-C₃alkynyl, halogen, cyano and nitro;    -   R²⁵ is hydrogen or C₁-C₆ alkyl;    -   R²⁶ is hydrogen or C₁-C₆ alkyl; and    -   G is selected from the group consisting of hydrogen,        —(CH₂)_(n)—R^(a), —C(O)—R^(a), —C(O)—(CR^(c)R^(d))_(n)—O—R^(b),        —C(O)—(CR^(c)R^(d))_(n)—S—R^(b), —C(O)NR^(a)R^(a), —S(O)₂—R^(a)        and C₁-C₈alkoxy-C₁-C₃alkyl-;    -   R^(a) is independently selected from the group consisting of        hydrogen, C₁-C₈alkyl, C₁-C₃haloalkyl, C₂-C₈alkenyl,        C₂-C₈alkynyl, C₃-C₆cycloalkyl, heterocyclyl and phenyl wherein        said heterocyclyl and phenyl groups are optionally substituted        by one, two or three substituents independently selected from        the group consisting of C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,        C₂-C₃alkenyl, C₂-C₃alkynyl, halogen, cyano and nitro;    -   R^(b) is selected from the group consisting of C₁-C₈alkyl,        C₁-C₃haloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, C₃-C₆ cycloalkyl,        heterocyclyl and phenyl wherein said heterocyclyl and phenyl        groups are optionally substituted by one, two or three        substituents independently selected from the group consisting of        C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₂-C₃alkenyl,        C₂-C₃alkynyl, halogen, cyano and nitro;    -   R^(c) is hydrogen or C₁-C₃ alkyl;    -   R^(d) is hydrogen or C₁-C₃ alkyl; and    -   n is independently 0, 1 or 2;    -   or an agriculturally acceptable salt thereof.

Alkyl groups (e.g C₁-C₆alkyl) include, for example, methyl (Me, CH₃),ethyl (Et, C₂H₅), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu),isobutyl (i-Bu), sec-butyl (s-Bu) and tert-butyl (t-Bu).

Alkenyl and alkynyl moieties can be in the form of straight or branchedchains, and the alkenyl moieties, where appropriate, can be of eitherthe (E)- or (Z)-configuration. Examples are vinyl, ally) and propargyl.Alkenyl and alkynyl moieties can contain one or more double and/ortriple bonds in any combination.

Halogen (or halo) encompasses fluorine, chlorine, bromine or iodine. Thesame correspondingly applies to halogen in the context of otherdefinitions, such as haloalkyl.

Haloalkyl groups (e.g C₁-C₆haloalkyl) are, for example, fluoromethyl,difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl,pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl,2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, heptafluoro-n-propyland perfluoro-n-hexyl.

Alkoxy groups (e.g C₁-C₄alkoxy-) are, for example, methoxy, ethoxy,propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy,preferably methoxy and ethoxy.

Alkoxyalkyl groups (e.g C₁-C₈alkoxy-C₁-C₃alkyl-) includes, for example,methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl,n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Cycloalkyl groups (e.g C₃-C₆cycloalkyl-) include, for examplecyclopropyl (c-propyl, c-Pr), cyclobutyl (c-butyl, c-Bu), cyclopentyl(c-pentyl) and cyclohexyl (c-hexyl) and may be substituted orunsubstituted as indicated.

C₁-C₆alkyl-S— (alkylthio) is, for example, methylthio, ethylthio,propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio ortert-butylthio, preferably methylthio or ethylthio.

C₁-C₆alkyl-S(O)— (alkylsulfinyl) is, for example, methylsulfinyl,ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl,isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferablymethylsulfinyl or ethylsulfinyl.

C₁-C₆alkyl-S(O)₂— (alkylsulfonyl) is, for example, methylsulfonyl,ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl,isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferablymethylsulfonyl or ethylsulfonyl.

Heterocyclyl, unless stated otherwise, is a 5- or 6-memberedheterocyclyl which may be aromatic, saturated or partially saturated andcan contain from 1 to 4 heteroatoms each independently selected from thegroup consisting of oxygen, nitrogen and sulphur.

The invention also relates agriculturally acceptable salts of thecompounds of Formula (I). Such salts include those which are able toform with amines, alkali metal and alkaline earth metal bases orquaternary ammonium bases. Among the alkali metal and alkaline earthmetal hydroxides as salt formers, special mention should be made of thehydroxides of lithium, sodium, potassium, magnesium and calcium, butespecially the hydroxides of sodium and potassium. The compounds ofFormula (I) according to the invention also include hydrates which maybe formed during the salt formation.

Examples of amines suitable for ammonium salt formation include ammoniaas well as primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkylamines, for examplemethylamine, ethylamine, n-propylamine, isopropylamine, the fourbutylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,methylhexylamine, methylnonylamine, methylpentadecylamine,methyloctadecylamine, ethylbutylamine, ethylheptylamine,ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine,diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine,dioctylamine, ethanolamine, n-propanolamine, isopropanolamine,N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, n-but-2-enylamine, n-pent-2-enylamine,2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine,propylenediamine, trimethylamine, triethylamine, tri-n-propylamine,triisopropylamine, tri-n-butylamine, triisobutylamine,tri-sec-butylamine, tri-n-amylamine, methoxyethylamine andethoxyethylamine; heterocyclic amines, for example pyridine, quinoline,isoquinoline, morpholine, piperidine, pyrrolidine, indoline,quinuclidine and azepine; primary arylamines, for example anilines,methoxyanilines, ethoxyanilines, o-, m- and p-toluidines,phenylenediamines, benzidines, naphthylamines and o-, m- andp-chloroanilines; but especially triethylamine, isopropylamine anddiisopropylamine.

In one embodiment of the present invention R¹ is 1-propynyl.

-   -   In another embodiment of the present invention R¹ is phenyl        optionally substituted by one or two R¹⁵ substituents, e.g        selected from the group consisting of cyano, chloro and fluoro.    -   In another embodiment of the present invention R¹ is a 5 or 6        membered heteroaryl which comprises one or two nitrogen        heteroatoms, said heteroaryl optionally substituted by one or        two R¹⁵ substituents, e.g selected from the group consisting of        cyano, chloro and fluoro. In a preferred embodiment, said        heteroaryl is selected from the group consisting of pyridyl,        pyrimidinyl, and pyrazolyl.

In one embodiment of the present invention R² is preferably chloro.

In one embodiment of the present invention R³ is methoxy.

In another embodiment of the present invention R³ is chloro.

In one embodiment of the present invention, R⁴ is C₁-C₂alkoxy- (e.gmethoxy or ethoxy).

In another embodiment of the present invention R⁴ is —C(═O)C₁-C₃alkyl(e.g —C(C═O)methyl, —C(C═O)ethyl, —C(C═O)i-propyl).

In another embodiment of the present invention, R⁴ is—C(═O)C₁-C₃haloalkyl, more preferably —C(═O)C₁-C₂fluoroalkyl e.g—C(═O)CH₂F, —C(═O)CHF₂, —C(═O)CF₃).

In one embodiment of the present invention, R⁴ is —S(O)_(n)C₁-C₆alkylespecially —S(O)₂methyl or —S(O)₂ethyl In another embodiment R⁴ is—S(O)_(n)C₁-C₆haloalkyl, for example —S(O)₂chloromethyl.

In another embodiment R⁴ is —S(O)_(n)—(CH₂)_(n)—C₃-C₆cycloalkyl, forexample —S(O)₂—(CH₂)-c-propyl.

In another embodiment of the present invention, R⁴ is —C(O)OC₁-C₆alkyl,especially —C(O)—O-methyl.

In another embodiment of the present invention, R⁴ is—S(O)_(n)C(R¹¹)R¹²R¹³ or —C(O)C(R¹¹)R¹²R¹³ wherein R¹¹ is hydrogen ormethyl and R¹²R¹³ taken together are —CH₂OCH₂— (oxetan-3-yl).

In another embodiment of the present invention, R⁴ is—C(O)—(CH₂)_(n)—C₃-C₆cycloalkyl, for example —C(O)-c-propyl or—C(O)—(CH₂)-c-propyl.

In another embodiment of the present invention, R⁴ is —C(O)(CR⁹R¹⁰)CN,for example —C(O)CH₂CN, —C(O)CH(CH₃)CN or —C(O)C(CH₃)₂CN.

In another embodiment of the present invention, R⁴ is—C(O)(CH₂)_(n)S(O)_(n)C₁-C₆alkyl, for example —C(O)CH₂S(O)₂methyl.

In another embodiment of the present invention, R⁴ is—C(O)C₁-C₃alkoxyC₁-C₆alkyl, for example —C(O)CH₂CH₂—O—CH₃or—C(O)CH(CH₃)—O—CH₃.

In another embodiment of the present invention, R⁴ is —C(O)NR⁵R⁶,especially wherein R⁵ is hydrogen and R⁶ is C₁-C₆ alkyl e.g t-butyl.

In another embodiment of the present invention, R⁴ is—C(O)—(CH₂)_(n)—NR⁷C(O)R⁸, for example —C(O)—(CH₂)—NR⁷C(O)R⁸ or—C(O)NR⁷C(O)R⁸, for example —C(O)NHC(O)-t-butyl.

In another embodiment of the present invention, R⁴ is selected from thegroup consisting of -phenyl, —C(O)-phenyl, —S(O)_(n)phenyl wherein eachphenyl is optionally substituted as defined previously.

In another embodiment of the present invention R⁴ is heterocyclyl, —C(O)heterocyclyl or —S(O)_(n)-heterocyclyl. In another embodiment, eachaforementioned heterocyclyl is an aromatic heterocyclyl (i.eheteroaryl), more preferably selected from the group consisting offuranyl, pyrrolyl, thiophenyl, imidazolyl, pyrazolyl, oxazolyl,isoxazolyl, thiazolyl, pyranyl, pyridyl, pyrazinyl, pyrimidinyl,pyridazinyl, and triazolyl more preferably selected from the groupconsisting of pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl each ofwhich is optionally substituted as defined previously. In anotherembodiment, each aforementioned heterocyclyl is a partially saturatedheterocyclyl, more preferably selected from the group consisting ofimidazolinyl, isoxazolinyl and thiazolinyl each of which is optionallysubstituted as defined previously. In another embodiment, eachaforementioned heterocyclyl is a saturated heterocyclyl more preferablyselected from the group consisting of morpholinyl, tetrahydrofuryl andtetrahydropyranyl each of which is optionally substituted as definedpreviously.

In one embodiment of the present invention, G is selected from the groupconsisting of hydrogen, C₁-C₈alkyl (e.g methyl, ethyl, n-propyl,i-propyl, n-butyl, t-butyl, —C₂-C₈alkenyl (e.g vinyl), C₂-C₈alkynyl (e.gpropargyl), —C(O)C₁-C₈alkyl (more preferably —C(O)C₁-C₆alkyl e.g—C(O)i-propyl and —C(O)t-butyl) and —C(O)—O—C₁-C₆alkyl (more preferably—C(O)—O—C₁-C₆alkyl e.g —C(O)—O-methyl). In a preferred embodiment, G ishydrogen.

Depending on the nature of the substituents, compounds of Formula (I)may exist in different isomeric forms. When G is hydrogen, for example,compounds of Formula (I) may exist in different tautomeric forms.

This invention covers all such isomers and tautomers and mixturesthereof in all proportions. Also, when substituents contain doublebonds, cis- and trans-isomers can exist. These isomers, too, are withinthe scope of the claimed compounds of the Formula (I). Compounds ofFormula (I) may contain asymmetric centres and may be present as asingle enantiomer, pairs of enantiomers in any proportion or, where morethan one asymmetric centre are present, contain diastereoisomers in allpossible ratios. Typically one of the enantiomers has enhancedbiological activity compared to the other possibilities.

The compounds of Formula (I) according to the invention can be used asherbicides by themselves, but they are generally formulated intoherbicidal compositions using formulation adjuvants, such as carriers,solvents and surface-active agents (SFAs). Thus, the present inventionfurther provides a herbicidal composition comprising a herbicidalcompound according to any one of the previous claims and anagriculturally acceptable formulation adjuvant. The composition can bein the form of concentrates which are diluted prior to use, althoughready-to-use compositions can also be made. The final dilution isusually made with water, but can be made instead of, or in addition to,water, with, for example, liquid fertilisers, micronutrients, biologicalorganisms, oil or solvents.

The herbicidal compositions generally comprise from 0.1 to 99% byweight, especially from 0.1 to 95% by weight, compounds of Formula (I)and from 1 to 99.9% by weight of a formulation adjuvant which preferablyincludes from 0 to 25% by weight of a surface-active substance.

The compositions can be chosen from a number of formulation types, manyof which are known from the Manual on Development and Use of FAOSpecifications for Plant Protection Products, 5th Edition, 1999. Theseinclude dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), aerosols, capsule suspensions (CS) and seed treatmentformulations. The formulation type chosen in any instance will dependupon the particular purpose envisaged and the physical, chemical andbiological properties of the compound of Formula (I).

Dustable powders (DP) may be prepared by mixing a compound of Formula(I) with one or more solid diluents (for example natural clays, kaolin,pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulphur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of Formula (I)with one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulphate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of Formula(I) with one or more solid diluents or carriers, one or more wettingagents and, preferably, one or more dispersing agents and, optionally,one or more suspending agents to facilitate the dispersion in liquids.The mixture is then ground to a fine powder. Similar compositions mayalso be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of acompound of Formula (I) and one or more powdered solid diluents orcarriers, or from pre formed blank granules by absorbing a compound ofFormula (I) (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of Formula (I) (or a solution thereof, in a suitable agent) onto a hard core material (such as sands, silicates, mineral carbonates,sulphates or phosphates) and drying if necessary. Agents which arecommonly used to aid absorption or adsorption include solvents (such asaliphatic and aromatic petroleum solvents, alcohols, ethers, ketones andesters) and sticking agents (such as polyvinyl acetates, polyvinylalcohols, dextrins, sugars and vegetable oils). One or more otheradditives may also be included in granules (for example an emulsifyingagent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof Formula (I) in water or an organic solvent, such as a ketone, alcoholor glycol ether. These solutions may contain a surface active agent (forexample to improve water dilution or prevent crystallisation in a spraytank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of Formula (I) in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment.

Preparation of an EW involves obtaining a compound of Formula (I) eitheras a liquid (if it is not a liquid at room temperature, it may be meltedat a reasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents which have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound ofFormula (I) is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in in ECs or in EWs. An ME may be either anoil-in-water or a water-in-oil system (which system is present may bedetermined by conductivity measurements) and may be suitable for mixingwater-soluble and oil-soluble pesticides in the same formulation. An MEis suitable for dilution into water, either remaining as a microemulsionor forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound ofFormula (I). SCs may be prepared by ball or bead milling the solidcompound of Formula (I) in a suitable medium, optionally with one ormore dispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of Formula (I) may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Aerosol formulations comprise a compound of Formula (I) and a suitablepropellant (for example n-butane). A compound of Formula (I) may also bedissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurised, hand-actuated spray pumps.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerisationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of Formula (I) and, optionally, a carrier or diluenttherefor. The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound ofFormula (I) and they may be used for seed treatment. A compound ofFormula (I) may also be formulated in a biodegradable polymeric matrixto provide a slow, controlled release of the compound.

The composition may include one or more additives to improve thebiological performance of the composition, for example by improvingwetting, retention or distribution on surfaces; resistance to rain ontreated surfaces; or uptake or mobility of a compound of Formula (I).Such additives include surface active agents (SFAs), spray additivesbased on oils, for example certain mineral oils or natural plant oils(such as soy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a compound of Formula (I).

Wetting agents, dispersing agents and emulsifying agents may be SFAs ofthe cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), salts of sulphonated aromatic compounds (for example sodiumdodecylbenzenesulphonate, calcium dodecylbenzenesulphonate,butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ethersulphates (for example sodium laureth-3-sulphate), ether carboxylates(for example sodium laureth-3-carboxylate), phosphate esters (productsfrom the reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulphosuccinamates, paraffin or olefine sulphonates, taurates andlignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

The herbicidal compounds of present invention can also be used inmixture with one or more additional herbicides and/or plant growthregulators. Examples of such additional herbicides or plant growthregulators include acetochlor, acifluorfen (includingacifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid,aminotriazole, atrazine, bensulfuron (including bensulfuron-methyl),bentazone, bicyclopyrone, bilanafos, bispyribac-sodium, bixlozone,bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (includingcarfentrazone-ethyl), cloransulam (including cloransulam-methyl),chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron,cinmethylin, clacyfos, clethodim, clodinafop (includingclodinafop-propargyl), clomazone, clopyralid, cyclopyranil,cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl),2,4-D (including the choline salt and 2-ethylhexyl ester thereof),2,4-DB, desmedipham, dicamba (including the aluminium, aminopropyl,bis-aminopropylmethyl, choline, dichloroprop, diglycolamine,dimethylamine, dimethylammonium, potassium and sodium salts thereof)diclosulam, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P,diquat dibromide, diuron, ethalfluralin, ethofumesate, fenoxaprop(including fenoxaprop-P-ethyl), fenoxasulfone, fenquinotrione,fentrazamide, flazasulfuron, florasulam, florpyrauxifen (includingflorpyraxifen-benzyl), fluazifop (including fluazifop-P-butyl),flucarbazone (including flucarbazone-sodium), flufenacet, flumetsulam,flumioxazin, flupyrsulfuron (including flupyrsulfuron-methyl-sodium),fluroxypyr (including fluroxypyr-meptyl), fomesafen, foramsulfuron,glufosinate (including the ammonium salt thereof), glyphosate (includingthe diammonium, isopropylammonium and potassium salts thereof),halauxifen (including halauxifen-methyl), haloxyfop (includinghaloxyfop-methyl), hexazinone, hydantocidin, imazamox, imazapic,imazapyr, imazethapyr, indaziflam, iodosulfuron (includingiodosulfuron-methyl-sodium), iofensulfuron (includingiofensulfuron-sodium), ioxynil, isoproturon, isoxaflutole, lancotrione,MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl),mesotrione, metamitron, metazachlor, methiozolin, metolachlor,metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron,norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride,pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden,pretilachlor, primisulfuron-methyl, propanil, propaquizafop,propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil,pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyridate,pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac,quinmerac, quizalofop (including quizalofop-P-ethyl andquizalofop-P-tefuryl), rimsulfuron, saflufenacil, sethoxydim, simazine,S metalochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione,tembotrione, terbuthylazine, terbutryn, thiencarbazone, thifensulfuron,tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone,triallate, triasulfuron, tribenuron (including tribenuron-methyl),triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium),trifludimoxazin, trifluralin, triflusulfuron,4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one,4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one,5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one,4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one,4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one,(4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one,3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione,2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione,2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione,2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione,6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione,2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione,2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione,2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione,3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione,2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione,6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione,2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione,4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dioneand 4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione.

The mixing partners of the compound of Formula (I) may also be in theform of esters or salts, as mentioned e.g. in The Pesticide Manual,Sixteenth Edition, British Crop Protection Council, 2012.

The compound of Formula (I) can also be used in mixtures with otheragrochemicals such as fungicides, nematicides or insecticides, examplesof which are given in The Pesticide Manual.

The mixing ratio of the compound of Formula (I) to the mixing partner ispreferably from 1:100 to 1000:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of Formula (I) with the mixing partner).

The compounds or mixtures of the present invention can also be used incombination with one or more herbicide safeners. Examples of suchsafeners include benoxacor, cloquintocet (including cloquintocet-mexyl),cyprosulfamide, dichlormid, fenchlorazole (includingfenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen(including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl),metcamifen and oxabetrinil.

Particularly preferred are mixtures of a compound of Formula (I) withcyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or metcamifen.

The safeners of the compound of Formula (I) may also be in the form ofesters or salts, as mentioned e.g. in The Pesticide Manual, 16^(th)Edition (BCPC), 2012. The reference to cloquintocet-mexyl also appliesto a lithium, sodium, potassium, calcium, magnesium, aluminium, iron,ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof asdisclosed in WO 02/34048.

Preferably the mixing ratio of compound of Formula (I) to safener isfrom 100:1 to 1:10, especially from 20:1 to 1:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of Formula (I) with the safener).

The present invention still further provides a method of controllingweeds at a locus comprising crop plants and weeds, wherein the methodcomprises application to the locus of a weed controlling amount of acomposition according to the present invention. ‘Controlling’ meanskilling, reducing or retarding growth or preventing or reducinggermination. Generally the plants to be controlled are unwanted plants(weeds). ‘Locus’ means the area in which the plants are growing or willgrow.

The rates of application of compounds of Formula (I) may vary withinwide limits and depend on the nature of the soil, the method ofapplication (pre- or post-emergence; seed dressing; application to theseed furrow; no tillage application etc.), the crop plant, the weed(s)to be controlled, the prevailing climatic conditions, and other factorsgoverned by the method of application, the time of application and thetarget crop. The compounds of Formula (I) according to the invention aregenerally applied at a rate of from 10 to 2000 g/ha, especially from 50to 1000 g/ha.

The application is generally made by spraying the composition, typicallyby tractor mounted sprayer for large areas, but other methods such asdusting (for powders), drip or drench can also be used.

Useful plants in which the composition according to the invention can beused include crops such as cereals, for example barley and wheat,cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet,sugar cane and turf.

Crop plants can also include trees, such as fruit trees, palm trees,coconut trees or other nuts. Also included are vines such as grapes,fruit bushes, fruit plants and vegetables.

Crops are to be understood as also including those crops which have beenrendered tolerant to herbicides or classes of herbicides (e.g. ALS-,GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methodsof breeding or by genetic engineering. An example of a crop that hasbeen rendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding is Clearfield® summer rape (canola). Examples ofcrops that have been rendered tolerant to herbicides by geneticengineering methods include e.g. glyphosate- and glufosinate-resistantmaize varieties commercially available under the trade namesRoundupReady® and LibertyLink®.

Crops are also to be understood as being those which have been renderedresistant to harmful insects by genetic engineering methods, for exampleBt maize (resistant to European corn borer), Bt cotton (resistant tocotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).Examples of Bt maize are the Bt 176 maize hybrids of NK® (SyngentaSeeds). The Bt toxin is a protein that is formed naturally by Bacillusthuringiensis soil bacteria. Examples of toxins, or transgenic plantsable to synthesise such toxins, are described in EP-A-451 878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examplesof transgenic plants comprising one or more genes that code for aninsecticidal resistance and express one or more toxins are Knockout®(maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton),NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seedmaterial thereof can be both resistant to herbicides and, at the sametime, resistant to insect feeding (“stacked” transgenic events). Forexample, seed can have the ability to express an insecticidal Cry3protein while at the same time being tolerant to glyphosate.

Crops are also to be understood to include those which are obtained byconventional methods of breeding or genetic engineering and containso-called output traits (e.g. improved storage stability, highernutritional value and improved flavour).

Other useful plants include turf grass for example in golf-courses,lawns, parks and roadsides, or grown commercially for sod, andornamental plants such as flowers or bushes.

The compositions can be used to control unwanted plants (collectively,‘weeds’). The weeds to be controlled may be both monocotyledonousspecies, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus,Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria,Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, anddicotyledonous species, for example Abutilon, Amaranthus, Ambrosia,Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida,Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium. The compoundsof the present invention have been shown to exhibit particularly goodactivity against certain grass weed species, especially Lolium Perenne.Weeds can also include plants which may be considered crop plants butwhich are growing outside a crop area (‘escapes’), or which grow fromseed left over from a previous planting of a different crop(‘volunteers’). Such volunteers or escapes may be tolerant to certainother herbicides.

The compounds of the present invention can be prepared according to thefollowing schemes.

Compounds of formula (I) wherein G is other than hydrogen may beprepared by treating a compound of formula (I) wherein G is hydrogen,with a reagent G-Z, wherein G-Z is an alkylating agent such as an alkylhalide, acylating agent such as an acid chloride or anhydride,sulfonylating agent such as a sulfonyl chloride, carbamylating agentsuch as a carbamoyl chloride, or carbonating agent such as achloroformate, using known methods.

Compounds of formula (I) may be prepared by reacting an iodonium ylideof formula (A), wherein Ar is an optionally substituted phenyl group,and an aryl boronic acid of formula (B), in the presence of a suitablepalladium catalyst, a base and in a suitable solvent.

Suitable palladium catalysts are generally palladium(II) or palladium(0)complexes, for example palladium(II) dihalides, palladium(II) acetate,palladium(II) sulfate, bis(triphenylphosphine)-palladium(II) dichloride,bis(tricyclopentylphosphine)-palladium(II) dichloride,bis(tricyclohexyl-phosphine)palladium(II) dichloride,bis(dibenzylideneacetone)palladium(0) ortetrakis-(triphenylphosphine)palladium(0). The palladium catalyst canalso be prepared “in situ” from palladium(II) or palladium(0) compoundsby complexing with the desired ligands, by, for example, combining thepalladium(II) salt to be complexed, for example palladium(II) dichloride(PdCl₂) or palladium(II) acetate (Pd(OAc)₂), together with the desiredligand, for example triphenylphosphine (PPh₃), tricyclopentylphosphine,tricyclohexylphosphine, 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenylor 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl and theselected solvent, with a compound of formula (A), the arylboronic acidof formula (B), and a base. Also suitable are bidendate ligands, forexample 1,1′-bis(diphenylphosphino)ferrocene or1,2-bis(diphenylphosphino)ethane. By heating the reaction medium, thepalladium(11) complex or palladium(0) complex desired for the C—Ccoupling reaction is thus formed “in situ”, and then initiates the C Ccoupling reaction.

The palladium catalysts are used in an amount of from 0.001 to 50 mol %,preferably in an amount of from 0.1 to 15 mol %, based on the compoundof formula (A). The reaction may also be carried out in the presence ofother additives, such as tetralkylammonium salts, for example,tetrabutylammonium bromide. Preferably the palladium catalyst ispalladium acetate, the base is lithium hydroxide and the solvent isaqueous 1,2-dimethoxyethane.

A compound of formula (A) may be prepared from a 1,3 dione compound offormula (C) by treatment with a hypervalent iodine reagent such as a(diacetoxy)iodobenzene or an iodosylbenzene and a base such as aqueoussodium carbonate, lithium hydroxide or sodium hydroxide in a solventsuch as water or an aqueous alcohol such as aqueous ethanol using knownprocedures.

Alternatively, the R¹ group may be added later in the synthetic sequenceby decarboxylative propynylation (where R¹ is propyne) or alternativeSuzuki/Stille or similar cross coupling where R¹ is phenyl or heteroaryl(either directly from aryl halide of formula (E) or via conversion toboronic acid (AA)) as shown in the scheme below.

Boronic acids can be prepared by methods such as below in Scheme 5. Forexample, a compound of formula (B) or (D) may be prepared from an arylhalide of formula (F) or (H) by known methods. For example, an arylhalide of formula (G) or (H) may be treated with an alkyl lithium oralkyl magnesium halide in a suitable solvent, preferably diethyl etheror tetrahydrofuran, at a temperature of between −80° C. and 30° C., andthe aryl magnesium or aryl lithium reagent obtained may then be reactedwith a trialkyl borate (preferably trimethylborate) to give an aryldialkylboronate which may be hydrolysed to provide a boronic acid offormula (B) or (D) under acidic conditions.

Compounds of formula (I) can also be prepared via Pb coupling as shownin the scheme below by reacting a compound of formula (D), to form anorganolead reagent of formula (J) and subsequent reaction with 1,3 dione(C) under conditions described, for example, by J. Pinhey, Pure andAppl. Chem., (1996), 68 (4), 819 and by M. Moloney et al., TetrahedronLett., (2002), 43, 3407. A suitable triarylbismuth compound underconditions described, for example, by A. Yu. Fedorov et al., Russ. Chem.Bull. Int. Ed., (2005), 54 (11), 2602, and by P. Koech and M. Krische,J. Am. Chem. Soc., (2004), 126 (17), 5350 and references therein may beused as a related procedure.

The compounds of type (I) can also be prepared via palladium coupling asshown in the scheme below, where boronic acid of type (B) is coupled tothe suitably protected halo-alkene of type (K) in a Suzuki typecoupling.

With suitable conditions, a suitable 1,3 dione may also be directlycoupled to a halo-compound (for example of formula (L)) with palladiumcatalysis. Propynylation or arylation/heteroarylation of intermediate(M) as described earlier gives compounds of type (I).

A compound of formula (I, G=H) may be prepared by the cyclisation of acompound of formula (O), wherein R is hydrogen or an alkyl group,preferably in the presence of an acid or base, and optionally in thepresence of a suitable solvent, by analogous methods to those describedby T. Wheeler, U.S. Pat. No. 4,209,532. The compounds of formula (O)have been particularly designed as intermediates in the synthesis of thecompounds of the Formula (I). A compound of formula (O) wherein R ishydrogen may be cyclised under acidic conditions, preferably in thepresence of a strong acid such as sulfuric acid, polyphosphoric acid orEaton's reagent, optionally in the presence of a suitable solvent suchas acetic acid, toluene or dichloromethane.

Compounds of type (I) can also be made by late stage functionalisationwith use of a suitable protecting group as shown in the scheme below.Compound (Q) can be converted to intermediate (R) by the methodsdescribed and then the protecting group (such as the BOC group shown)can be removed (under acidic conditions in this example). Intermediate(S) can then be directly converted to compounds (for example (U) ordoubly reacted on both oxygen and nitrogen atoms to give compounds oftype (T). Compounds of type (T) can readily be converted to any compoundof type (I)—for example the enol-ester of (T) can be selectivityhydrolysed to give (U, G=H), which can be then converted to (U, G isother than H) by the methods described earlier.

Alternatively, the sequence can be performed with sulfonylation ratherthan acylation.

Ureas, acyl ureas, N-Heteroaryl and N-cyano compounds can be made fromintermediate (S), also by standard literature methods as known tosomeone skilled in the art, such as in scheme 12.

1,3-Diones such as these may be prepared using methods such as thatshown below. So commercially available ketones (for example of type (Y))can be converted into intermediate (Q) (these methods are described inWO2008/110308).

The following non-limiting examples provide specific synthesis methodsfor representative compounds of the present invention, as referred to inTable 1 below.

EXAMPLE 13-benzoyl-9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione(Example A3)

Step 1: Synthesis of O3-tert-butyl 011-ethyl8,10-dioxo-3-azaspiro[5.5]undecane-3,11-dicarboxylate

Tert-Butyl 4-acetonylidenepiperidine-1-carboxylate (12.9 g, 54.0 mmol)was dissolved in ethanol (100 mL) and diethyl propanedioate (54.12 mmol)was added. The reaction mixture was treated with a solution of sodiumethoxide which had been prepared by the addition of sodium (54.1 mmol)to ethanol (30 mL) at room temperature. The reaction mixture was stirredat RT for 3 hours then heated to reflux for 1 hour. Upon cooling thereaction mixture was concentrated in vacuo to give O3-tert-butyl011-ethyl 8,10-dioxo-3-azaspiro[5.5]undecane-3,11-dicarboxylate as anoil, which was used in the next step without further purification.

Step 2: Synthesis of tert-butyl8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

Crude O3-tert-butyl 011-ethyl8,10-dioxo-3-azaspiro[5.5]undecane-3,11-dicarboxylate from step 1 wasdissolved in aqueous NaOH (12M, 5 mL) and stirred for 5 hours. Thereaction mixture was acidified to pH 6 by the addition of conc HCl at 0°C., and extracted with EtOAc. The organics were dried and concentratedin vacuo to leave a yellow solid which on trituration yielded a palepink powder of tert-butyl8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate. The aqueous layer wasfurther acidified to pH 2 by the addition of conc HCl and extracted withEtOAc. The organics were dried and concentrated in vacuo to leave a paleyellow solid which on trituration with ether gave a further batch ofpale yellow powder of tert-butyl8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (3.914 g, 13.91 mmol).

1H NMR (400 MHz, CDCl₃) 3.51-3.25 (m, 6H), 2.69-2.54 (m, 4H), 1.47-1.43(m, 9H), 1.44-1.39 (m, 4H).

Step 3: Synthesis of tert-butyl9-(4-bromo-2-chloro-6-methoxy-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

To a stirred solution of tert-butyl8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (8.56 g, 30.4 mmol) inchloroform (320.0 mL) under nitrogen was added 4-Dimethylaminopyridine(23.2 g, 190 mmol). The reaction mixture was stirred for 15 mins at RT,then toluene (65.0 mL) was added followed by the addition of[diacetoxy-(4-bromo-2-chloro-6-methoxy-phenyl)plumbyl] acetate (for asynthesis see WO 2014096289) (23.0 g, 38.0 mmol). The reaction mixturewas stirred at 80° C. for 4 h and then at RT overnight. The reactionmixture was cooled in an ice water bath, acidified with citric acidsolution, filtered through celite pad. The filtrate was layer separatedand the aqueous layer extracted with chloroform (×3). The combinedorganics were washed with brine, dried over Na₂SO₄, filtered andfiltrate evaporated to obtained crude product, which was purified byflash column chromatography to give tert-butyl9-(4-bromo-2-chloro-6-methoxy-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(6.2 g) as a brown foam.

LCMS(NH4OAc:ACN): M−H=500

Step 4: Synthesis of tert-butyl9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

A mixture of tert-butyl9-(4-bromo-2-chloro-6-methoxy-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(0.960 g, 1.92 mmol), and 4-diphenylphosphanylbutyl(diphenyl)phosphane(0.163 g, 0.383 mmol, and Bis(triphenylphosphine)palladium(II) chloride(0.135 g, 0.192 mmol) and 2-Butynoic acid (0.483 g, 5.75 mmol) was takenin a round bottomed flask. A vacuum/argon back fill cycle was repeatedfor two times, then treated with anhydrous DMSO (20 mL) and againvacuum/argon back fill cycle repeated for three times then1,8-Diazabicyclo[5.4.0]undec-7-ene (1.75 g, 11.5 mmol) was added. Thereaction mixture was stirred at 110° C. overnight and then the reactionmixture was allowed stand for the weekend at RT. The reaction mixturewas acidified with 10% citric acid solution and extracted with EtOAc(×3). The combined organics were dried over Na₂SO₄, filtered andconcentrated to obtain crude product as a brown gummy liquid.

LC-MS: (M+H=460, RT=2.87)

Step 5: Synthesis of9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azoniaspiro[5.5]undecane-8,10-dionehydrochloride

A mixture of tert-butyl9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(4.60 g, 10.0 mmol) was stirred at RT in HCl in Dioxane (4M, 25.0 mL)for 2 h. The reaction mixture was concentrated and triturated with EtOActo obtain 3.90 g of9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azoniaspiro[5.5]undecane-8,10-dionehydrochloride as an off white solid LC-MS: M+H=360

Step 6:3-benzoyl-9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione(Example A3)

To a mixture of9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dionehydrochloride (0.25 g, 0.5236 mmol), benzoic acid (0.06394 g, 0.5236mmol) and HATU (0.220 g, 0.5760 mmol) in anhydrous DCM (3.46 g, 2.618mL, 40.6 mmol) was added N,N-diisopropylethylamine (0.204 g, 0.270 mL,1.571 mmol). The resulting mixture was stirred at RT overnight. Thereaction mixture was poured into 2M HCl and extracted with DCM. Theorganics were passed through a phase-sep cartridge and the filtrateevaporated. The crude residue was submitted to FractionLynxreverse-phase HPLC purification (TFA method), product containingfractions were isolated and then freeze-dried overnight to give3-benzoyl-9-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-3-azaspiro[5.5]undecane-8,10-dione(example A3) (113 mg, 47%) as a white solid.

1H NMR (400 MHz, Methanol-d4) δ=7.50-7.38 (m, 5H), 7.00 (br s, 1H), 6.87(br s, 1H), 3.87-3.60 (m, 5H), 3.47 (m, 2H), 2.61-2.60 (m, 4H), 2.02 (s,3H), 1.85-1.65 (m, 4H)

EXAMPLE 26-[4-[3-(cyclopropanecarbonyl)-8,10-dioxo-3-azaspiro[5.5]undecan-9-yl]-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile(Example A51)

Step 1: Synthesis of tert-butyl 8,10-dioxo-9-(phenyl-$I″{circumflex over( )}{3}-iodanylidene)-3-azaspiro[5.5]undecane-3-carboxylate

A solution of tert-butyl8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (915 mg, 3.252 mmol)and sodium carbonate (532 mg, 6.23 mmol) in water (11.8 mL) and ethanol(2.5 mL) was treated with (diacetoxyiodo)benzene (1.00 g, 2.961 mmol)and stirred at RT overnight. The precipitate was collected by filtrationand washed with water and diethyl ether to give tert-butyl8,10-dioxo-9-(phenyl-$1{3}-iodanylidene)-3-azaspiro[5.5]undecane-3-carboxylate(1.37 g, 91%) as a white solid.

1H NMR (400 MHz, Methanol-d4) δ=7.85 (d, 2H), 7.55 (t, 1H), 7.40 (t,2H), 3.46-3.34 (m, 4H), 2.58 (s, 4H), 1.52-1.46 (m, 4H), 1.44 (s, 9H)

Step 2: Synthesis of tert-butyl9-(4-bromo-2-ethyl-6-methyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

A mixture of (4-bromo-2-ethyl-6-methyl-phenyl)boronic acid (1.78 g,5.869 mmol), tert-butyl8,10-dioxo-9-(phenyl-$1{3}-iodanylidene)-3-azaspiro[5.5]undecane-3-carboxylate(1.374 g, 2.701 mmol), palladium(II) acetate (32 mg, 0.1425 mmol) andlithium hydroxide (377 mg, 15.7424 mmol) was treated with1,2-dimethoxyethane (18 mL) and water (3 mL) The reaction vessel wasevacuated and back-filled with nitrogen three times and the mixture wasstirred at 50° C. overnight. The mixture was then allowed to cool to RTbefore being concentrated, taken up in water, acidified with aqueousammonium chloride and extracted with dichloromethane. The organics weredried, concentrated and purified by flash column chromatography to givetert-butyl9-(4-bromo-2-ethyl-6-methyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(808 mg, 53%) as a brown gum.

1H NMR (400 MHz, CDCl₃) δ=7.30 (s, 2H), 5.42 (s, 1H), 3.57-3.41 (m, 4H),2.60 (s, 2H), 2.53 (s, 2H), 2.43-2.28 (m, 2H), 2.06 (s, 3H), 1.69-1.61(m, 4H), 1.47 (s, 9H), 1.08 (t, 3H)

Step 3: Synthesis of tert-butyl9-[2-ethyl-6-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

A mixture of tert-butyl9-(4-bromo-2-ethyl-6-methyl-phenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(300 mg, 0.533 mmol), bis(pinacolato)diboron (172 mg, 0.643 mmol),1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloridedichloromethane complex (47 mg, 0.056 mmol) and potassium acetate (109mg, 1.09 mmol) was treated with 1,4-dioxane (5.3 mL, 61 mmol, 99 mass %,120). The vessel was evacuated and back-filled with nitrogen three timesand the mixture was stirred at 100° C. for 4 hours. On cooling, thereaction mixture was concentrated and purified by flash columnchromatography to give tert-butyl9-[2-ethyl-6-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(338 mg, 84%) as an orange gum.

1H NMR (400 MHz, CDCl₃) δ=7.60 (d, 2H), 5.41-5.39 (m, 1H), 3.58-3.39 (m,4H), 2.63-2.58 (m, 2H), 2.53 (s, 2H), 2.47-2.33 (m, 2H), 2.10 (s, 3H),1.70-1.62 (m, 4H), 1.49-1.46 (m, 9H), 1.35 (s, 12H), 1.08 (t, 3H)

Step 4: Synthesis of tert-butyl9-[4-(5-cyano-2-pyridyl)-2-ethyl-6-methyl-phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

A mixture of tert-butyl9-[2-ethyl-6-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(338 mg, 0.450 mmol), 2-bromo-5-cyanopyridine (121 mg, 0.628 mmol),1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloridedichloromethane complex (84 mg, 0.100 mmol) and potassium phosphatetribasic (383 mg, 1.804 mmol) was treated with 1,2-dimethoxyethane (4.5mL) and water (2.3 mL). The reaction vessel was evacuated andback-filled with nitrogen three times and the mixture was stirred at 80°C. for an hour. On cooling, the mixture was diluted with 10% aqueouscitric acid and extracted with dichloromethane. The organics were dried,concentrated and purified by flash column chromatography to givetert-butyl9-[4-(5-cyano-2-pyridyl)-2-ethyl-6-methyl-phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(213 mg, 85%) as a pale yellow solid.

1H NMR (400 MHz, CDCl3) δ=8.93 (dd, 1H), 8.01 (dd, 1H), 7.84 (dd, 1H),7.79 (d, 2H), 5.58-5.52 (m, 1H), 3.57-3.41 (m, 4H), 2.69-2.61 (m, 2H),2.59-2.54 (m, 2H), 2.53-2.43 (m, 2H), 2.23-2.17 (m, 3H), 1.73-1.64 (m,4H), 1.48 (s, 9H), 1.15 (t, 3H)

Step 5: Synthesis of6-[4-(8,10-dioxo-3-azaspiro[5.5]undecan-9-yl)-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrilehydrochloride

A solution of tert-butyl9-[4-(5-cyano-2-pyridyl)-2-ethyl-6-methyl-phenyl]-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate(213 mg, 0.382 mmol) in dichloromethane (2.0 mL) was treated with 4Mhydrogen chloride in dioxane (1.0 mL, 4.0 mmol) and was stirred at RTfor 2.5 hours. The mixture was concentrated and the residues weretriturated from diethyl ether to give6-[4-(8,10-dioxo-3-azaspiro[5.5]undecan-9-yl)-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrilehydrochloride (260 mg, 100%) as a pale yellow solid.

1H NMR (400 MHz, Methanol-d4) δ=9.00-8.94 (m, 1H), 8.23 (dd, 1H), 8.08(d, 1H), 7.86-7.76 (m, 2H), 3.38-3.26 (m, 4H), 2.71 (s, 4H), 2.48 (q,2H), 2.16 (s, 3H), 1.98-1.92 (m, 4H), 1.14 (t, 3H)

Step 6: Synthesis of6-[4-[3-(cyclopropanecarbonyl)-8,10-dioxo-3-azaspiro[5.5]undecan-9-yl]-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile(Example A51)

A suspension of6-[4-(8,10-dioxo-3-azaspiro[5.5]undecan-9-yl)-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile;dihydrochloride (260 mg, 0.382 mmol) and HATU (182 mg, 0.476 mmol) indichloromethane (6.0 mL) was treated with triethyamine (260 μL, 1.93mmol) and cyclopropanecarboxylic acid (50 μL, 0.628 mmol) and themixture was stirred at RT for an hour. The mixture was concentrated,diluted with 0.5 M hydrochloric acid and extracted with dichloromethane.The organics were dried, concentrated and purified by flash columnchromatography to give6-[4-[3-(cyclopropanecarbonyl)-8,10-dioxo-3-azaspiro[5.5]undecan-9-yl]-3-ethyl-5-methyl-phenyl]pyridine-3-carbonitrile(156 mg, 82%) as a cream coloured solid.

1H NMR (400 MHz, Methanol-d4) δ=8.93 (d, 1H), 8.17 (dd, 1H), 8.04 (d,1H), 7.81 (s, 1H), 7.79 (s, 1H), 3.91-3.78 (m, 2H), 3.73-3.61 (m, 2H),2.66 (s, 4H), 2.54-2.43 (q, 2H), 2.16 (s, 3H), 2.05-1.94 (m, 1H),1.88-1.77 (m, 2H), 1.75-1.63 (m, 2H), 1.13 (t, 3H), 0.94-0.77 (m, 4H).

Examples of herbicidal compounds of the present invention.

TABLE 1 CMP Structure NMR A1

1H NMR (400 MHz, CDCl₃) 7.11 (s, 1H), 6.84 (s, 1H), 3.73 (s, 3H),3.69-3.55 (m, 2H), 3.49 (s, 2H), 2.57 (s, 4H), 2.12 (s, 3H), 2.06 (s,3H), 1.82-1.62 (m, 4H) A2

1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.85 (s, 1H), 3.69 (s,3H), 3.34-3.30 (4H), 3.07-3.02 (q, 2H), 2.51 (s, 4H), 2.01 (s, 3H),1.81-1.75 (m, 4H), 1.34-1.28 (m, 3H) A3

1H NMR (400 MHz, Methanol-d4) δ = 7.50- 7.38 (m, 5H), 7.00 (br s, 1H),6.87 (br s, 1H), 3.87-3.60 (m, 5H), 3.47 (m, 2H), 2.61- 2.60 (m, 4H),2.02 (s, 3H), 1.85-1.65 (m, 4H) A4

1H NMR (400 MHz, Methanol-d4) δ = 8.58- 8.57 (d, 1H), 7.89 (t, 1H),7.55-7.49 (d, 1H), 7.43 (t, 1H), 6.96 (s, 1H), 6.86 (s, 1H), 3.65 (s,3H), 3.54-3.44 (m, 4H), 2.45 (s, 4H), 2.04 (s, 3H), 1.66 (bs, 4H) A5

1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.86 (s, 1H), 4.15 (s,2H), 3.69 (s, 3H), 3.62-3.60 (m, 2H), 3.49 (m, 2H), 3.39 (s, 3H), 2.55(s, 4H), 2.01 (s, 3H), 1.78-1.66 (m, 4H) A6

1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.86 (s, 1H), 3.69 (s,3H), 3.38 (m, 4H), 2.51 (s, 4H), 2.01 (s, 3H), 1.70-1.63 (m, 4H), 1.32(s, 9H) A7

1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.85 (s, 1H), 3.69 (s,3H), 3.51 (bs, 4H), 2.54 (s, 4H), 2.01 (s, 3H), 1.78-1.72 (m, 4H), 1.22(s, 9H) A8

1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 6.86 (s, 1H), 3.79 (bs,2H), 3.69 (s, 3H), 3.62 (bs, 2H), 2.56 (s, 4H), 2.01 (s, 3H), 1.97-1.96(m, 1H), 1.80- 1.76 (m, 2H), 1.68-1.65 (m, 2H), 0.86-0.85 (ill.res.d,2H), 0.81- 0.79 (d, 2H) A9

1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 6.87 (s, 1H), 6.47 (t,1H), 3.70-3.62 (m, 7H), 2.57 (s, 4H), 2.01 (s, 3H), 1.81-1.71 (m, 4H)A10

1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.86 (s, 1H), 3.70-3.66(m, 7H), 2.54 (s, 4H), 2.01 (s, 3H), 1.73-1.66 (m, 4H), 1.27 (s, 9H) A11

1H NMR (400 MHz, Methanol-d4) δ = 8.68- 8.67 (d, 1H), 8.19-8.17 (d, 1H),8.03-7.99 (m, 1H), 7.64-7.61 (m, 1H), 6.99 (s, 1H), 6.86 (s, 1H), 3.69(s, 3H), 3.64 (m, 4H), 2.57 (s, 4H), 2.01 (s, 3H), 1.84-1.77 (m, 4H) A12

1H NMR (400 MHz, Methanol-d4) δ = 6.98 (s, 1H), 6.86 (s, 1H), 3.61 (s,3H), 3.45 (bs, 2H), 3.31 (bs, 2H), 2.42 (s, 4H), 2.02 (s, 3H), 1.61 (m,2H), 1.52 (m, 2H) A13

1H NMR (400 MHz, Methanol-d4) δ = 8.96- 8.95 (ill.res.d, 1H), 8.22- 8.19(dd, 1H), 8.11-8.09 (d, 1H), 7.78 (s, 1H), 7.66 (s, 1H), 3.83 (s, 3H),3.63 (t, 2H), 3.57 (t, 2H), 2.57 (s, 4H), 2.11-2.10 (3H), 1.81-1.77 (m,2H), 1.70 (t, 2H) A14

1H NMR (400 MHz, Methanol-d4) δ = 7.34 (s, 2H), 3.62 (t, 2H), 3.56 (t,2H), 2.60 (s, 4H), 2.09 (s, 3H), 2.03 (s, 3H), 1.78 (t, 2H), 1.68 (t,2H) (m, 4H) A15

1H NMR (400 MHz, Methanol-d4) δ = 7.34 (s, 2H), 3.88 (s, 2H), 3.64 (t,2H), 3.49 (t, 2H), 2.61 (s, 4H), 2.03 (s, 3H), 1.80 (t, 2H), 1.72 (t,2H) A16

1H NMR (400 MHz, Methanol-d4) δ = 7.34 (s, 2H), 6.46 (t, 1H), 3.69-3.62(m, 4H), 2.63 (s, 4H), 2.03 (s, 3H), 1.82-1.74 (m, 4H) A17

1H NMR (400 MHz, Methanol-d4) δ = 8.67 (d, 1H), 8.18 (d, 1H), 8.02 (t,1H), 7.64-7.63 (m, 1H), 7.34 (s, 2H), 3.65 (t, 4H), 2.63 (s, 4H), 2.03(s, 3H), 1.83 (t, 4H) A18

1H NMR (400 MHz, Methanol-d4) δ = 7.30 (s, 2H), 6.48 (t, 1H), 4.62 (s,2H), 3.68-3.57 (m, 2H), 3.51-3.43 (m, 2H), 2.49 (s, 4H), 2.02 (s, 3H),1.78-1.70 (m, 4H) A19

1H NMR (400 MHz, Methanol-d4) δ = 8.93 (s, 1H), 8.26 (d, 1H), 7.78 (d,1H), 6.99 (d, 1H), 6.86 (d, 1H), 3.83- 3.81 (m, 2H), 3.69 (d, 3H),3.46-3.45 (m, 2H), 2.64-2.60 (m, 4H), 2.02 (s, 3H), 1.87-1.81 (m, 2H),1.77-1.72 (m, 2H) A20

1H NMR (400 MHz, Methanol-d4) δ = 8.65 (br s, 2H), 7.45 (d, 2H), 6.99(d, 1H), 6.86 (d, 1H), 3.83-3.77 (m, 2H), 3.68 (d, 3H), 3.42-3.33 (m,2H), 2.67-2.52 (m, 4H), 2.02 (s, 3H), 1.88- 1.78 (m, 2H), 1.72-1.69 (m,2H) A21

1H NMR (400 MHz, Methanol-d4) δ = 8.63 (s, 2H), 7.90 (d, 1H), 7.52 (t,1H), 6.99 (s, 1H), 6.86 (s, 1H), 3.82 (br s, 2H), 3.70-3.66 (br d, 3H),3.47 (br s, 2H), 2.60 (s, 4H), 2.02 (s, 3H), 1.82-1.72 (m, 4H) A22

1H NMR (400 MHz, Methanol-d4) δ = 9.27- 9.23 (m, 1H), 7.91-7.83 (m, 2H),6.99 (d, 1H), 6.86 (d, 1H), 3.90-3.82 (m, 2H), 3.69 (d, 3H), 3.56-3.43(m, 2H), 2.66- 2.57 (m, 4H), 2.02 (s, 3H), 1.86-1.77 (m, 4H) A23

1H NMR (400 MHz, Methanol-d4) δ = 8.17 (t, 1H), 7.90-7.84 (m, 2H), 6.99(d, 1H), 6.86 (d, 1H), 3.84-3.82 (m, 2H), 3.69 (d, 3H), 3.54-3.45 (m,2H), 2.64-2.56 (m, 4H), 2.02 (s, 3H), 1.88- 1.80 (m, 2H), 1.78-1.75 (m,2H) A24

1H NMR (400 MHz, Methanol-d4) δ = 7.77 (t, 1H), 7.14 (d, 1H), 7.00 (d,1H), 6.87 (d, 2H), 3.92 (d, 3H), 3.83-3.78 (m, 2H), 3.69 (d, 3H),3.60-3.54 (m, 2H), 2.64- 2.54 (m, 4H), 2.02 (s, 3H), 1.82-1.78 (m, 4H)A25

1H NMR (400 MHz, Methanol-d4) δ = 8.26 (d, 1H), 7.58 (d, 1H), 7.51-7.45(m, 1H), 6.99 (br s, 1H), 6.86 (br s, 1H), 3.91 (s, 3H), 3.79 (br s,2H), 3.69 (d, 3H), 3.54 (br s, 2H), 2.98 (s, 4H), 2.02 (s, 3H), 1.85-1.68 (m, 4H) A26

1H NMR (400 MHz, Methanol-d4) δ = 8.38 (d, 1H), 7.12 (s, 1H), 7.05 (d,1H), 6.99 (d, 1H), 6.86 (d, 1H), 3.92 (s, 3H), 3.83-3.76 (m, 2H), 3.69(d, 3H), 3.45- 3.37 (m, 2H), 2.64-2.55 (m, 4H), 2.02 (s, 3H), 1.86-1.79(m, 2H), 1.78- 1.66 (m, 2H) A27

1H NMR (400 MHz, Methanol-d4) δ = 8.31 (d, 1H), 7.33 (d, 1H), 7.14 (s,1H), 7.00 (d, 1H), 6.86 (d, 1H), 3.83- 3.77 (m, 2H), 3.69 (d, 3H),3.42-3.36 (m, 2H), 2.64-2.55 (m, 4H), 2.02 (s, 3H), 1.88-1.68 (m, 4H)A28

1H NMR (400 MHz, Methanol-d4) δ = 8.69 (s, 1H), 8.54 (s, 1H), 6.99 (d,1H), 6.86 (d, 1H), 3.85-3.79 (m, 2H), 3.69 (d, 3H), 3.60-3.53 (m, 2H),2.64-2.55 (m, 7H), 2.01 (s, 3H), 1.87- 1.71 (m, 4H) A29

1H NMR (400 MHz, Methanol-d4) δ = 7.76 (d, 1H), 7.27 (d, 1H), 7.00 (d,1H), 6.87 (d, 1H), 4.14 (s, 3H), 3.88- 3.80 (m, 2H), 3.69 (d, 3H),3.62-3.55 (m, 2H), 2.65-2.56 (m, 4H), 2.02 (s, 3H), 1.89-1.74 (m, 4H)A30

1H NMR (400 MHz, DMSO-d6) δ = 8.58 (br s, 1H), 8.47 (br s, 1H), 6.97 (d,1H), 6.86 (d, 1H), 3.69 (br s, 2H), 3.61 (d, 3H), 3.15 (br s, 2H),2.50-2.40 (m, 7H), 2.05 (s, 3H), 1.72-1.50 (m, 4H) A31

1H NMR (400 MHz, Methanol-d4) δ = 7.52- 7.45 (m, 1H), 7.42-7.36 (m, 1H),7.31-7.25 (m, 1H), 7.23-7.16 (m, 1H), 6.99 (d, 1H), 6.85 (d, 1H),3.89-3.80 (m, 2H), 3.68 (d, 3H), 3.41-3.33 (m, 2H), 2.64-2.52 (m, 4H),2.03-2.00 (m, 3H), 1.88-1.65 (m, 4H) A32

1H NMR (400 MHz, Methanol-d4) δ = 7.69- 7.61 (m, 2H), 7.50-7.39 (m, 5H),7.23 (br s, 1H), 7.17 (t, 2H), 7.07 (br s, 1H), 3.88-3.70 (m, 5H), 3.48(br s, 2H), 2.63 (s, 4H), 1.90-1.66 (m, 4H) A33

1H NMR (400 MHz, Methanol-d4) δ = 8.78 (s, 2H), 8.06 (s, 1H), 7.94 (s,1H), 7.49-7.40 (m, 5H), 3.89-3.75 (m, 5H), 3.48 (br s, 2H), 2.63 (s,4H), 1.90-1.67 (m, 4H) A34

1H NMR (400 MHz, Methanol-d4) δ = 8.96 (d, 1H), 8.20 (dd, 1H), 8.10 (d,1H), 7.78 (s, 1H), 7.66 (s, 1H), 7.48- 7.39 (m, 5H), 3.88-3.76 (m, 5H),3.48 (br s, 2H), 2.70-2.55 (m, 4H), 1.90- 1.67 (m, 4H) A35

1H NMR (400 MHz, Methanol-d4) δ = 8.98- 8.97 (m, 1H), 8.22 (dd, 1H),8.12 (dd, 1H), 7.80 (d, 1H), 7.68 (d, 1H), 3.85 (s, 3H), 3.85-3.80 (m,2H), 3.68-3.61 (m, 2H), 2.63 (s, 4H), 2.03- 1.95 (m, 1H), 1.86-1.66 (m,4H), 0.92-0.74 (m, 4H) A36

1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.85 (s, 1H), 5.97-5.89(m, 1H), 5.30 (d, 1H), 5.19 (d, 1H), 4.20 (s, 2H), 4.04 (d, 2H), 3.69(s, 3H), 3.66- 3.59 (m, 2H), 3.55-3.47 (m, 2H), 2.53 (s, 4H), 2.02 (s,3H), 1.79-1.64 (m, 4H) A37

1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 6.86 (s, 1H), 3.70 (s,3H), 3.66-3.59 (m, 2H), 3.58-3.52 (m, 2H), 2.79-2.71 (m, 1H), 2.57 (s,4H), 2.02 (s, 3H), 1.81-1.69 (m, 4H), 0.81-0.75 (m, 2H), 0.59- 0.54 (m,2H) A38

1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 6.87 (s, 1H), 4.18 (s,2H), 3.70 (s, 3H), 3.65-3.59 (m, 2H), 3.58-3.50 (m, 2H), 3.45 (t, 2H),2.56 (s, 4H), 2.02 (s, 3H), 1.80-1.59 (m, 6H), 0.94 (t, 3H) A39

1H NMR (400 MHz, Methanol-d4) δ = 7.00 (s, 1H), 7.87 (s, 1H), 3.70 (s,3H), 3.66-3.63 (m, 2H), 3.59-3.54 (m, 2H), 3.49 (q, 2H), 2.56 (s, 4H),2.02 (s, 3H), 1.82-1.64 (m, 4H) A40

1H NMR (400 MHz, Methanol-d4) δ = 7.38 (d, 2H), 7.02-6.96 (m, 3H), 6.86(s, 1H), 3.83 (s, 3H), 3.80-3.48 (m, 7H), 2.58 (s, 4H), 2.01 (s, 3H),1.75 (br s, 4H) A41

1H NMR (400 MHz, Methanol-d4) δ = 7.36 (t, 1H), 7.05-6.93 (m, 4H), 6.85(s, 1H), 3.82 (s, 3H), 3.78 (br s, 2H), 3.72-3.63 (m, 3H), 3.46 (br s,2H), 2.57 (s, 4H), 2.01 (s, 3H), 1.87-1.78 (m, 2H), 1.76-1.63 (m, 2H)A42

1H NMR (400 MHz, Methanol-d4) δ = 7.41 (t, 1H), 7.21 (d, 1H), 7.09- 6.96(m, 3H), 6.85 (d, 1H), 3.85 (s, 3H), 3.79 (t, 2H), 3.68 (d, 3H), 3.33(m, 2H), 2.62-2.48 (m, 4H), 2.01 (s, 3H), 1.82-1.56 (m, 4H) A43

1H NMR (400 MHz, Methanol-d4) δ = 7.94 (d, 1H), 7.81 (d, 1H), 7.00 (s,1H), 6.87 (s, 1H), 4.32 (br s, 2H), 3.81 (br s, 2H), 3.70 (s, 3H), 2.60(s, 4H), 2.02 (s, 3H), 1.86-1.78 (m, 4H) A44

1H NMR (400 MHz, Methanol-d4) δ = 7.48 (d, 1H), 7.00 (d, 1H), 6.87 (d,1H), 6.47 (d, 1H), 3.90 (s, 3H), 3.84- 3.56 (m, 7H), 2.60 (s, 4H), 2.02(s, 3H), 1.86- 1.68 (m, 4H) A45

1H NMR (400 MHz, Methanol-d4) δ = 8.78 (s, 1H), 7.00 (d, 1H), 6.86 (s,1H), 6.69 (s, 1H), 3.85-3.79 (m, 2H), 3.74-3.65 (m, 5H), 2.59 (s, 4H),2.02 (s, 3H), 1.86-1.63 (m, 4H) A46

1H NMR (400 MHz, Methanol-d4) δ = 6.99 (s, 1H), 6.87 (s, 1H), 3.69 (s,3H), 3.33-3.24 (m, 4H), 2.83 (s, 6H), 2.54 (s, 4H), 2.02 (s, 3H),1.75-1.67 (m, 4H) A47

1H NMR (400 MHz, Methanol-d4) δ = 7.05 (d, 2H), 3.69-3.53 (m, 4H), 2.60(s, 4H), 2.38- 2.29 (q, 2H), 2.11 (s, 3H), 2.03-1.97 (m, 6H), 1.79-1.71(m, 2H), 1.71- 1.62 (m, 2H), 1.04 (t, 3H) A48

1H NMR (400 MHz, Methanol-d4) δ = 7.07 (s, 2H), 3.66-3.54 (m, 4H), 2.60(s, 4H), 2.34 (q, 4H), 2.11 (s, 3H), 2.01 (s, 3H), 1.78-1.71 (m, 2H),1.70-1.62 (m, 2H), 1.04 (t, 6H) A49

1H NMR (400 MHz, Methanol-d4) δ = 7.23 (s, 1H), 7.16 (s, 1H), 3.68-3.53(m, 4H), 2.60 (s, 4H), 2.39 (q, 2H), 2.10 (s, 3H), 2.02 (s, 3H),1.87-1.79 (m, 1H), 1.77-1.69 (m, 2H), 1.68- 1.61 (m, 1H), 1.06 (t, 3H)A50

1H NMR (400 MHz, Methanol-d4) δ = 6.87 (s, 1H), 6.78 (d, 1H), 3.67 (d,3H), 3.65-3.59 (m, 2H), 3.59-3.53 (m, 2H), 2.58 (s, 4H), 2.33 (q, 2H),2.11 (s, 3H), 2.01 (s, 3H), 1.82-1.76 (m, 1H), 1.75-1.67 (m, 2H),1.66-1.59 (m, 1H), 1.04 (t, 3H) A51

1H NMR (400 MHz, Methanol-d4) δ = 8.93 (d, 1H), 8.17 (dd, 1H), 8.04 (d,1H), 7.81 (s, 1H), 7.79 (s, 1H), 3.91- 3.78 (m, 2H), 3.73-3.61 (m, 2H),2.66 (s, 4H), 2.54-2.43 (q, 2H), 2.16 (s, 3H), 2.05-1.94 (m, 1H),1.88-1.77 (m, 2H), 1.75-1.63 (m, 2H), 1.13 (t, 3H), 0.94-0.77 (m, 4H)A52

1H NMR (400 MHz, Methanol-d4) δ = 8.94 (dd, 1H), 8.18 (dd, 1H), 8.06(dd, 1H), 7.82 (s, 2H), 3.90-3.79 (m, 2H), 3.73-3.61 (m, 2H), 2.67 (s,4H), 2.48 (q, 4H), 2.05-1.95 (m, 1H), 1.85- 1.76 (m, 2H), 1.74-1.66 (m,2H), 1.14 (t, 6H), 0.92-0.76 (m, 4H) A53

1H NMR (400 MHz, Methanol-d4) δ = 8.96 (dd, 1H), 8.21 (dd, 1H), 8.09 (d,1H), 8.03 (d, 1H), 7.93 (d, 1H), 3.88- 3.79 (m, 2H), 3.72-3.61 (m, 2H),2.66 (s, 4H), 2.53 (q, 2H), 2.05-1.95 (m, 1H), 1.93-1.85 (m, 1H),1.83-1.73 (m, 2H), 1.72-1.62 (m, 1H), 1.14 (t, 3H), 0.93-0.76 (m, 4H)A54

1H NMR (400 MHz, Methanol-d4) δ = 8.94 (d, 1H), 8.18 (dd, 1H), 8.08 (d,1H), 7.60 (d, 1H), 7.56 (d, 1H), 3.88- 3.74 (m, 5H), 3.72-3.61 (m, 2H),2.63 (s, 4H), 2.49 (q, 2H), 2.04-1.95 (m, 1H), 1.90-1.82 (m, 1H),1.81-1.70 (m, 2H), 1.70-1.62 (m, 1H), 1.14 (t, 3H), 0.92-0.77 (m, 4H)A55

1H NMR (400 MHz, DMSO-d6) δ = 7.22 (s, 1H), 7.17 (s, 1H), 3.50- 3.39 (m,4H), 2.04 (s, 3H), 2.01-1.98 (m, 6H), 1.70-1.63 (m, 1H), 1.62- 1.52 (m,2H), 1.51-1.45 (m, 1H) A56

1H NMR (400 MHz, DMSO-d6) δ = 9.11 (d, 1H), 8.41 (dd, 1H), 8.25 (d, 1H),8.03 (d, 1H), 7.97 (d, 1H), 3.51-3.39 (m, 4H), 2.55 (br s, 4H), 2.14 (s,3H), 2.00 (s, 3H), 1.74-1.66 (m, 1H), 1.65-1.56 (m, 2H), 1.55- 1.47 (m,1H) A57

1H NMR (400 MHz, DMSO-d6) δ = 9.11 (s, 1H), 8.42 (d, 1H), 8.26 (d, 1H),8.03 (s, 1H), 7.97 (s, 1H), 3.81-3.64 (m, 2H), 3.60-3.44 (m, 2H),2.68-2.54 (m, 4H), 2.16 (s, 3H), 2.05-1.90 (m, 1H), 1.81-1.42 (m, 4H),0.77-0.62 (m, 4H) A58

1H NMR (400 MHz, Methanol-d4) δ = 8.52 (s, 1H), 7.97-7.90 (m, 1H), 7.87(d, 1H), 7.75 (d, 1H), 7.72-7.62 (m, 1H), 3.88-3.79 (m, 2H), 3.69-3.60(m, 2H), 2.66 (s, 4H), 2.20 (s, 3H), 2.05-1.94 (m, 1H), 1.93- 1.84 (m,1H), 1.83-1.73 (m, 2H), 1.70-1.61 (m, 1H), 0.92-0.77 (m, 4H)

BIOLOGICAL EXAMPLES

Seeds of a variety of test species are sown in standard soil in pots(Lolium perenne (LOLPE), Setaria faberi (SETFA), Alopecurus myosuroides(ALOMY), Echinochloa crus-galli (ECHCG), Avena fatua (AVEFA)). Aftercultivation for one day (pre-emergence) or after 8 days cultivation(post-emergence) under controlled conditions in a glasshouse (at 24/16°C., day/night; 14 hours light; 65% humidity), the plants are sprayedwith an aqueous spray solution derived from the formulation of thetechnical active ingredient in acetone/water (50:50) solution containing0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5).Compounds are applied at 250 g/h. The test plants are then grown in aglasshouse under controlled conditions in a glasshouse (at 24/16° C.,day/night; 14 hours light; 65% humidity) and watered twice daily. After13 days for pre and post-emergence, the test is evaluated for thepercentage damage caused to the plant. The biological activities areshown in the following table on a five-point scale (5=80-100%; 4=60-79%;3=40-59%; 2=20-39%; 1=0-19%).

TABLE B1 LOLPE SETFA ALOMY ECHCG AVEFA Compound PRE POST PRE POST PREPOST PRE POST PRE POST A1  5 5 5 5 NT NT 5 5 5 5 A2  5 5 5 5 5 5 5 5 5 5A3  5 5 5 5 5 5 5 5 5 5 A4  5 5 5 5 5 5 5 5 5 5 A5  5 5 5 5 5 5 5 5 5 5A6  5 5 5 5 5 5 5 5 5 5 A7  5 5 5 5 5 5 5 5 5 5 A8  5 5 5 5 5 5 5 5 5 5A9  5 5 5 5 5 5 5 5 5 5 A10 5 5 5 5 5 5 5 5 5 5 A11 5 5 5 5 5 5 5 5 3 5A12 5 5 5 5 5 5 5 5 5 5 A13 1 5 2 5 3 5 5 5 2 5 A14 5 5 5 5 5 5 5 5 5 5A15 5 5 5 5 5 5 5 5 5 5 A16 5 5 5 5 5 5 5 5 5 5 A17 2 5 4 5 2 2 3 5 2 5A18 5 5 5 5 5 5 5 5 5 5 A35 5 5 5 5 5 5 5 5 5 5 A47 5 5 5 5 5 5 5 5 5 5A48 5 5 5 5 5 5 4 5 5 5 A49 5 5 5 5 5 5 5 5 5 5 A51 5 5 5 5 5 5 4 5 5 5A52 5 5 5 5 5 5 5 5 5 5 A53 5 5 5 5 5 5 5 5 5 5 A55 5 5 5 5 5 5 5 5 5 5A56 5 5 5 5 3 5 4 5 3 5 A57 5 5 5 5 5 5 5 5 5 5 A58 5 5 5 5 5 5 5 5 5 5NT = not tested.

1. A compound of Formula (I)

wherein R¹ is selected from methyl, ethynyl, 1-propynyl, phenyl and a 5or 6 membered heteroaryl which comprises one or two nitrogenheteroatoms, said phenyl and heteroaryl optionally substituted by one ortwo R¹⁵ substituents; R² is ethyl or chloro; R³ is selected from thegroup consisting of methyl, ethyl, methoxy and chloro; R⁴ is selectedfrom the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy-, C₁-C₄haloalkyl,—C(═O)C₁-C₄alkyl, —C(═O)C₁-C₄haloalkyl, —S(O)_(n)C₁-C₆alkyl,—S(O)_(n)C₁-C₆haloalkyl, —S(O)_(n)—(CH₂)_(n)—C₃-C₆cycloalkyl,—S(O)₁C(R¹¹)R¹²R¹³, —C(O)H, —C(O)—(CH₂)_(n)—C₃-C₆cycloalkyl,—C(O)C(R¹¹)R¹²R¹³, —C(O)C₂-C₄alkenyl, —C(O)(CR⁹R¹⁰)CN,—C(O)(CR⁹R¹⁰)(CR⁹R¹⁰)CN, —C(O)CH₂C(O)—C₁-C₆alkyl,—C(O)CH₂OC(O)—C₁-C₆alkyl, —C(O)OC₁-C₆alkyl, —C(O)OC₁-C₆haloalkyl,—C(O)(CH₂)_(n)S(O)_(n)C₁-C₆alkyl —C(O)C₁-C₃alkoxyC₁-C₆alkyl,—C(O)C₁-C₃alkoxyC₂-C₆alkenyl, —C(O)C₁-C₃alkoxyC₂-C₆alkynyl,—C(O)C₁-C₃alkoxyC₁-C₆haloalkyl, —C(O)C₁-C₃alkoxyC₃-C₆cycloalkyl,—C(O)OC₁-C₃alkoxyC₁-C₆alkyl, —C(O)C₁-C₃alkoxyC₁-C₃alkoxyC₁-C₆alkyl,—C(O)(CH₂)_(n)—NR⁵R⁶, —C(O)—(CH₂)_(n)—NR⁷C(O)R⁸,—C(O)—(CH₂)_(n)—O—N═CR⁵R⁵, —CN, —S(O)₂NR¹⁶R¹⁷, —S(O)(═NR¹⁸)R¹⁹,—C(O)C(O)R²⁰, —C(O)C(R²³)═N—O—R²⁴ or —C(O)C(R²³)═N—NR²⁵R²⁶,—(CH₂)_(n)-phenyl, —C(O)—(CH₂)_(n)-phenyl, —S(O)_(n)—(CH₂)_(n)-phenyl,-heterocyclyl, —C(O)—(CH₂)_(n)-heterocyclyl, —C(O)(CH₂)_(n)—(CH₂)_(n)heterocyclyl, —S(O)_(n)—(CH₂)_(n)-heterocyclyl, wherein eachheterocyclyl is a 5- or 6-membered heterocyclyl which may be aromatic,saturated or partially saturated and can contain from 1 to 4 heteroatomseach independently selected from the group consisting of oxygen,nitrogen and sulphur, and wherein said heterocyclyl or phenyl groups areoptionally substituted by one, two or three substituents independentlyselected from the group consisting of C₁-C₃alkyl, C₁-C₃haloalkyl,C₁-C₃alkoxy, C₂-C₃alkenyl, C₂-C₃alkynyl, halogen, cyano and nitro; R⁵ isindependently selected from the group consisting of hydrogen and C₁-C₆alkyl; R⁶ is selected from the group consisting of hydrogen, C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆haloalkyl, hydroxyl-, C₁-C₆alkoxy,C₃-C₆ cycloalkyl, —C₁-C₄alkoxyC₁-C₆alkyl, —C₁-C₃alkoxyC₁-C₆haloalkyl,—(CR⁹R¹⁰)C₁-C₆haloalkyl, —(CR⁹R¹⁰)C(O)NR⁵R⁵, phenyl, -pyridyl, whereinthe phenyl and pyridyl are optionally substituted by one, two or threesubstituents independently selected from the group consisting of C₁-C₃alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₂-C₃ alkenyl, C₂-C₃ alkynyl,halogen, cyano and nitro; or R⁵ and R⁶ together form —CH₂CH₂OCH₂CH₂—;and R⁷ is selected from the group consisting of hydrogen and C₁-C₆alkyl; R⁸ is selected from the group consisting of hydrogen, C₁-C₆alkyl, C₁-C₆ alkoxy, C₃-C₆ cycloalkyl, phenyl, -pyridyl, wherein thephenyl and pyridyl are optionally substituted by one, two or threesubstituents independently selected from the group consisting of C₁-C₃alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₂-C₃ alkenyl, C₂-C₃ alkynyl,halogen, cyano and nitro; R⁹ is hydrogen or methyl; R¹⁰ is hydrogen ormethyl; or R⁹ and R¹⁰ together form —CH₂CH₂—; and R¹¹ is hydrogen ormethyl; R¹² is selected from the group consisting of hydrogen, C₁-C₆alkyl, hydroxyl and C₁-C₆ alkoxy-; R¹³ is selected from the groupconsisting of hydrogen, C₁-C₆ alkyl, hydroxyl and C₁-C₆ alkoxy; or R¹²and R¹³ together form —CH₂—X—CH₂—; and X is selected from the groupconsisting of O, S and N—R¹⁴; R¹⁴ is selected from the group consistingof hydrogen, C₁-C₃ alkyl and C₁-C₃ alkoxy-; R¹⁵ is independentlyselected from the group consisting of C₁-C₄ alkyl, C₁-C₄ haloalkyl,cyano and halogen; R¹⁶ is hydrogen or C₁-C₆alkyl; and R¹⁷ is selectedfrom the group consisting of hydrogen, C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆ alkoxy-C₁-C₃alkyl-, —C(O)C₁-C₆alkyl, —C(O)OC₁-C₆alkyl and CH₂CN;or R¹⁶ and R¹⁷ together form —CH₂CH₂OCH₂CH₂—, —CH₂CH₂S(O)₂CH₂CH₂—; R¹⁸is hydrogen or C₁-C₆alkyl; R¹⁹ is selected from the group consisting ofhydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₃-C₆cycloalkyl, phenyl, -pyridyl,wherein the phenyl and pyridyl are optionally substituted by one, two orthree substituents independently selected from the group consisting ofC₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₂-C₃ alkenyl, C₂-C₃alkynyl, halogen, cyano and nitro; R²⁰ is selected from the groupconsisting of C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy-, C₁-C₆haloalkoxy,—NR²¹R²², phenyl and -pyridyl, wherein the phenyl and pyridyl areoptionally substituted by one, two or three substituents independentlyselected from the group consisting of C₁-C₃ alkyl, C₁-C₃ haloalkyl,C₁-C₃ alkoxy, C₂-C₃ alkenyl, C₂-C₃ alkynyl, halogen, cyano and nitro;R²¹ is selected from the group consisting of hydrogen, C₁-C₆ alkyl,C₁-C₆ alkoxy, C₁-C₆alkoxyC₁-C₃alkyl-, C₃-C₆ cycloalkyl, C₁-C₆haloalkyl-and C₁-C₆haloalkoxy-, —C(O)C₁-C₆alkyl, phenyl, -pyridyl, wherein thephenyl and pyridyl are optionally substituted by one, two or threesubstituents independently selected from the group consisting of C₁-C₃alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₂-C₃ alkenyl, C₂-C₃ alkynyl,halogen, cyano and nitro; R²² is hydrogen or C₁-C₆alkyl; or R²¹ and R²²together form —CH₂CH₂OCH₂CH₂—; R²³ is selected from the group consistingof hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy- andC₁-C₆haloalkoxy-; R²⁴ is selected from the group consisting of hydrogen,C₁-C₆alkyl, C₁-C₆alkoxyC₁-C₃alkyl-, C₃-C₆cycloalkyl, —CH₂CN,tetrahydropyranyl-, phenyl and -pyridyl, wherein the phenyl and pyridylare optionally substituted by one, two or three substituentsindependently selected from the group consisting of C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₂-C₃alkenyl, C₂-C₃alkynyl, halogen, cyanoand nitro; R²⁵ is hydrogen or C₁-C₆ alkyl; R²⁶ is hydrogen or C₁-C₆alkyl; and G is selected from the group consisting of hydrogen,—(CH₂)_(n)—R^(a), —C(O)—R^(a), —C(O)—(CR^(c)R^(d))_(n)—O—R^(b),—C(O)—(CR^(c)R^(d))_(n)—S—R^(b), —C(O)NR^(a)R^(a), —S(O)₂—R^(a) andC₁-C₃alkoxy-C₁-C₃alkyl-; R^(a) is independently selected from the groupconsisting of hydrogen, C₁-C₈alkyl, C₁-C₃haloalkyl, C₂-C₈alkenyl,C₂-C₈alkynyl, C₃-C₆cycloalkyl, heterocyclyl and phenyl wherein saidheterocyclyl and phenyl groups are optionally substituted by one, two orthree substituents independently selected from the group consisting ofC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₂-C₃alkenyl, C₂-C₃alkynyl,halogen, cyano and nitro; R^(b) is selected from the group consisting ofC₁-C₈alkyl, C₁-C₃haloalkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, C₃-C₆cycloalkyl, heterocyclyl and phenyl wherein said heterocyclyl and phenylgroups are optionally substituted by one, two or three substituentsindependently selected from the group consisting of C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₂-C₃alkenyl, C₂-C₃alkynyl, halogen, cyanoand nitro; R^(c) is hydrogen or C₁-C₃ alkyl; R^(d) is hydrogen or C₁-C₃alkyl; and n is independently 0, 1 or 2; or an agriculturally acceptablesalt thereof.
 2. A compound according to claim 1, wherein R¹ is1-propynyl.
 3. A compound according to claim 1, wherein R¹ is a 5 or 6membered heteroaryl which comprises one or two nitrogen heteroatoms,said phenyl and heteroaryl optionally substituted by one or two R¹⁵substituents.
 4. A compound according to claim 1, wherein R² is chloro.5. A compound according to claim 1, wherein R³ is methoxy.
 6. A compoundaccording to claim 1, wherein R³ is chloro.
 7. A compound according toclaim 1, wherein R⁴ is —C(═O)C₁-C₄alkyl.
 8. A compound according toclaim 1, wherein G is hydrogen.
 9. A compound according to claim 1,wherein G is —C(O)C₁-C₆alkyl.
 10. A compound according to claim 1,wherein G is —C(O)—O—C₁-C₆alkyl.
 11. A herbicidal composition comprisinga compound of Formula (I) according to claim 1 and an agriculturallyacceptable formulation adjuvant.
 12. A herbicidal composition accordingto claim 11, further comprising at least one additional pesticide.
 13. Aherbicidal composition according to claim 12, wherein the additionalpesticide is a herbicide or herbicide safener.
 14. A method ofcontrolling weeds at a locus comprising application to the locus of aweed controlling amount of a composition according to claim
 1. 15. Useof a compound of Formula (I) as defined in claim 1 as a herbicide.